CN109331820A - A kind of method that pulse electrodeposition prepares Pt base catalyst under ultrasound condition - Google Patents
A kind of method that pulse electrodeposition prepares Pt base catalyst under ultrasound condition Download PDFInfo
- Publication number
- CN109331820A CN109331820A CN201811264623.4A CN201811264623A CN109331820A CN 109331820 A CN109331820 A CN 109331820A CN 201811264623 A CN201811264623 A CN 201811264623A CN 109331820 A CN109331820 A CN 109331820A
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- CN
- China
- Prior art keywords
- base catalyst
- prepares
- pulse electrodeposition
- salt
- ultrasound condition
- Prior art date
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 117
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002604 ultrasonography Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 23
- 239000002608 ionic liquid Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 159
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 123
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 107
- 150000003839 salts Chemical class 0.000 claims description 99
- 239000000243 solution Substances 0.000 claims description 72
- 239000000725 suspension Substances 0.000 claims description 52
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- 229910052751 metal Inorganic materials 0.000 claims description 44
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- 239000002041 carbon nanotube Substances 0.000 claims description 40
- 235000019441 ethanol Nutrition 0.000 claims description 36
- 238000007747 plating Methods 0.000 claims description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 32
- 229910021389 graphene Inorganic materials 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 26
- -1 salt ion Chemical class 0.000 claims description 25
- 229920000557 Nafion® Polymers 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 23
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 20
- 229960004756 ethanol Drugs 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 17
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
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- 150000002739 metals Chemical class 0.000 claims description 11
- 229910052755 nonmetal Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 5
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 5
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229960003966 nicotinamide Drugs 0.000 claims description 5
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- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
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- 150000001412 amines Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 3
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 210000001367 artery Anatomy 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 210000003462 vein Anatomy 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 239000004698 Polyethylene Substances 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 2
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 claims 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000009938 salting Methods 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 23
- 239000000956 alloy Substances 0.000 description 23
- 238000009713 electroplating Methods 0.000 description 22
- 230000005611 electricity Effects 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 13
- 238000002203 pretreatment Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
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- 230000004913 activation Effects 0.000 description 11
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 229910002837 PtCo Inorganic materials 0.000 description 6
- 229910002836 PtFe Inorganic materials 0.000 description 6
- 229910002844 PtNi Inorganic materials 0.000 description 6
- 229910002849 PtRu Inorganic materials 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- 239000006260 foam Substances 0.000 description 3
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- 238000006722 reduction reaction Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910020427 K2PtCl4 Inorganic materials 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007714 electro crystallization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/464—Rhodium
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
A kind of method that pulse electrodeposition prepares Pt base catalyst under ultrasound condition, belongs to electro-deposition techniques field.This method combines the advantages of both pulse electrodeposition and ultrasound condition, by salting liquid needed for being prepared respectively in aqueous solution, organic solvent or ionic liquid as electroplate liquid, using carbon material as carrier, different pulse electrodeposition current densities, current switching time ratio (t are set using the pulse poweron/toff), the technological parameters such as temperature, electro-deposition prepares Pt base catalyst.For the present invention with pulse electrodeposition with both ultrasonic method preparation Pt base catalyst process combined is easy to operate, environmentally friendly, condition controllability is strong, Pt base catalyst average grain diameter obtained is small, large specific surface area and is firmly combined with carrier.
Description
Technical field
The invention belongs to electro-deposition techniques field, it is related to pulse electrodeposition under a kind of ultrasound condition and prepares Pt base catalyst
Method.
Background technique
Currently used for the catalyst of fuel cell, research it is the most mature be Pt precious metal catalyst using carbon material as carrier
Agent, but since Pt is expensive, and dissolution and aggregation easily occur in severe operating conditions, cause its electro catalytic activity with
Stability decline, is not achieved the requirement of fuel cell commercial catalyst.For Pt catalyst is expensive and catalyst poisoning
The problem of causing oxidation rate to decline, people have done many trials to improve Pt catalyst, and most effective one method is in Pt
The transition metal or nonmetallic of non-Pt noble metal, relative low price is mixed in catalyst, forms Pt base catalyst, it can be effective
The dosage for reducing precious metals pt, simultaneously because electronic effect or synergistic effect in catalyst between different component, can also show
Write the catalytic activity and CO tolerance for improving Pt.
Select suitable carrier, for improve Pt base catalyst activity, and then improve fuel battery performance to close weight
It wants.In Pt based catalyst carrier, most common carbon material carrier is active carbon Vulcan XC-72, in addition to this, carbon nanometer
Pipe and the novel carbon support material such as graphene because it is with the characteristics such as big specific surface area and the intensity that can weaken Pt-CO key,
Corrosion resistance and stability of the catalyst in high potential can be improved while significantly improving Pt nanoparticle dispersibility.
Chemical reduction method is as the method for commonly preparing Pt base catalyst, due to reducing agent and reaction system multiplicity, behaviour
Make it is simple, be it is a kind of can mass production Pt base catalyst synthetic method.But utilize the Pt base of chemical reduction method preparation
Particle aggregation problem easily occurs for catalyst, and easily there is a phenomenon where Pt base catalyst to fall off from carrier in use, from
And influence its catalytic effect.Therefore, consider from catalyst performance, reaction condition, environmental protection and production cost etc., exploitation one
Kind can guarantee that catalyst performance is excellent, reaction condition is mild, Pt base that is environmentally friendly and can reducing production cost to a certain extent is urged
Agent preparation method is of great significance.
Summary of the invention
The problem to be solved by the invention is to provide pulse electrodepositions under a kind of ultrasound condition to prepare the new of Pt base catalyst
Technology, is made with the technique of both ultrasonic method and simple and stable combined that average grain diameter is small, specific surface with pulse electrodeposition
Pt base catalyst that is long-pending big and being firmly combined with carrier.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of method that pulse electrodeposition prepares Pt base catalyst under ultrasound condition, this method combine pulse electrodeposition with
The advantages of both ultrasound conditions.By distinguishing alloyage salting liquid in aqueous solution, organic solvent or ionic liquid as electricity
Different pulse electrodeposition current densities, current switching time ratio is arranged using the pulse power using carbon material as carrier in plating solution
(ton/toff), the technological parameters such as temperature, honeycomb structure, porous nano cluster or particle are finally prepared on carbon material carrier
It is uniformly dispersed and has the Pt base catalyst of large specific surface area.Ultrasound condition of the present invention is in conjunction with pulse electrodeposition
Method, can not only make the nano particle of Pt base catalyst is uniform and stable to be supported on carbon material carrier, but also prepared
Journey is simple, reaction condition is mild, controllability is strong.
Preparation process of the invention specifically includes the following steps:
The first step, substrate material surface pretreatment
Basis material is successively carried out pre-treatment (oil removing, activation, washing, drying etc.), the catalyst electro-deposition base
Body material includes metal (nickel foam, copper, iron etc.), glass carbon, graphite, carbon paper, carbon cloth, electro-conductive glass etc..
Second step, prepares carbon material suspension, and carbon material includes activated carbon black, carbon nanotube and graphene
It prepares carbon slurry: the ratio of 1~10mg activated carbon black being added according to every milliliter of dehydrated alcohol, active carbon is added to nothing
In water-ethanol, the alcohol suspending liquid containing activated carbon black is made.According still further to the alcohol suspending liquid and Nafion solution of activated carbon black
Percent by volume be 1:100~6:100 ratio, be added volume fraction 5%Nafion solution, ultrasonic disperse 10~
120min forms carbon slurry.
Prepare carbon nanotube suspension: the volume ratio by the Nafion solution of volume fraction 5% and dehydrated alcohol according to 1:9
It is uniformly mixed and forms dispersion liquid, carbon nanotube, ultrasound is added according to the ratio that 1~20mg carbon nanotube is added in every milliliter of dispersion liquid
Disperse 10~120min, forms carbon nanotube suspension.
It prepares graphene suspension: the Nafion solution of volume fraction 5% and dehydrated alcohol is mixed according to the volume ratio of 1:9
Conjunction is formed uniformly dispersion liquid, and graphene, ultrasonic disperse 10 is added according to the ratio that 1~20mg graphene is added in every milliliter of dispersion liquid
~120min forms graphene suspension.
Third step, preparation work electrode
It is added dropwise according to the above-mentioned carbon slurry of 100~350 μ L, carbon nanotube suspension or the graphene suspension every square centimeter of pipetting
Onto the catalyst matrix surface handled well, after ethyl alcohol evaporating completely, by matrix in 20~100 DEG C be dried in vacuo 1~for 24 hours,
Pulse electrodeposition used working electrode in the process is made.
4th step prepares Pt base catalyst plating solution
Pt salt, the second component salt (metal salt or non-metal salt), additive are added in solvent, in 20~100 DEG C of items
Under part, reaction 1~make it completely dissolved afterwards for 24 hours is sufficiently stirred, obtains Pt base catalyst plating solution.The Pt salt and the second component
The molar ratio of metal or non-metal salt is 1:80~80:1.The concentration of Pt salt is 0.001~1mol/ in Pt base catalyst plating solution
L, the concentration of additive are 0~0.1mol/L, and the concentration of the metal salt of the second component is 0~5mol/L, the non-gold of the second component
The concentration for belonging to salt is 0~1mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, in the supersonic frequency of 20~200kHz, 0
Under the ultrasonic power of~3000W, pulse electrodeposition is carried out in the prepared Pt base catalyst plating solution of the 4th step, pulse current is close
Degree is 0.1~100mAcm-2, the make-and-break time ratio t of electric currenton/toffIt is 0.3~6, temperature is 20~100 DEG C, sedimentation time
For 1~7200s.The Pt base catalyst that electro-deposition obtains successively is used into dehydrated alcohol, distilled water clean the surface, and cold air drying.
Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
The Pt salt includes H2PtCl6·6H2O、K2(PtCl4)、K2PtCl6、Pt(acac)2、Pt(NO2)2(NH3)2、
H2Pt(NO2)2SO4、Na2Pt(OH)6And K2Pt(OH)6Deng.
Solvent in 4th step includes aqueous solution, organic solvent, ionic liquid.Wherein organic solvent includes first
The alcohols such as alcohol, ethyl alcohol；Ionic liquid include containing alkyl quaternary ammonium ion, alkyl quaternary alkylphosphonium salt ion, dialkyl group replace imidazoles from
The ionic liquid of son and the cation such as alkyl-substituted pyridinium ion of N- and contain PF6 -、BF4 -、[N(CFSO2)]-、CF3SO3 -、
AlCl4 -、CF3COO-、SbF6 -、Cl-、Br-、I-、NO3 -、ClO4 -Equal anion ion liquids.
Second component element includes non-platinum noble metals, transition metal or one of nonmetallic or multiple element.
Wherein, the non-platinum noble metals include Rh, Ru, Pd, Au, Ag etc., and the transition metal includes Fe, Co, Ni, Cu etc., institute
That states is nonmetallic including B, C, P, S, N etc..
The additive includes lauryl sodium sulfate, neopelex, sodium glycocholate, dioctyl succinate acid
Sodium sulfonate, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, polyethylene glycol, polyvinyl alcohol, butynediols,
Oleic acid, succimide, niacinamide, polyethyleneimine, polyvinylpyrrolidone, octyl phenol polyoxyethylene ether, alkyl alcohol
The mixture of the one or more arbitrary proportion such as polyoxyethylene ether, aliphatic amine polyoxyethylene ether, alkylol phthalein amine polyoxyethylene ether.
Compared with prior art, the invention has the benefit that
(1) method that pulse electrodeposition prepares Pt base catalyst under ultrasound condition of the present invention, unique distinction exist
In the combination of ultrasound condition and pulse electrodeposition, the process for preparing catalyst is easy to operate, environmentally friendly, condition controllability is strong, and
The Pt base catalyst average grain diameter arrived is smaller, stronger in conjunction with matrix.Ultrasonic wave itself not only has refinement to metal electrocrystallization
Crystal grain effect, and the refinement of nano particle can be further enhanced.The cavitation effect of ultrasonic wave can clean nano particle table
The gas and impurity of face absorption improve the wetting conditions that nano particle is deposited in electrode surface, while can also promote nanometer
Grain deposits on carbon carrier evenly dispersedly, to enhance the bond strength of nano particle and carbon carrier.
(2) present invention used in bath stability, electrodepositing speed is fast, permitted element main salt concentration range is wide, preparation
Pt base catalyst purity is high, be that Pt base catalyst that under ultrasound condition prepared by pulse electrodeposition is suitable for different catalysis and reacts
It is required that providing guarantee.
(3) present invention prepares Pt base catalyst using the method for pulse electrodeposition under ultrasound condition, with chemical reduction method, directly
The electro-deposition of galvanic electricity source, simple pulse electrodeposition are compared, and closer in conjunction with matrix, the smaller Pt base of average grain diameter is easily obtained
Catalyst.Emphasis has carried out power, frequency and the pulse of the molar ratio, ultrasound of Pt salt and the second component element salt in the present invention
The make-and-break time ratio t of the current density of electro-deposition, electric currenton/toff, depositing temperature, sedimentation time research, pass through process optimization
Obtain the Pt base catalyst that average grain diameter is smaller, pattern is more preferable, specific surface area is bigger.Other than traditional water is as solvent, this
Invention additionally uses organic solvent, ionic liquid as solvent, and the pulse electrodeposition at certain temperature and ultrasound condition plays
Organic solvent or both ionic liquid and electrodeposition method are preparing the advantage in Pt base catalyst, pass through the collaboration of the two
Common improving plating solution stability and catalyst performance are acted on, acquisition preparation method is simpler, crystal grain average grain diameter is smaller, specific surface
The bigger Pt base catalyst of product.
(4) present invention prepares Pt base catalyst using pulse electrodeposition method under ultrasound condition, and plating solution composition is simple, stability
It is good, be long placed in and ultrasound condition under after pulse electrodeposition, without precipitating, change colour phenomena such as.
Detailed description of the invention
Fig. 1 is the SEM test chart for the Pt base catalyst that embodiment 4 obtains.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawing, and however, it is not limited to this, all to this
Inventive technique scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered
Within the protection scope of the present invention.
Embodiment 1: pulse electrodeposition prepares PtRu/C catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (oil removing, activation, washing, drying etc.) is successively carried out to nickel foam substrate material.
Second step prepares carbon material suspension
It prepares carbon slurry: the ratio of 2mg activated carbon black being added according to every milliliter of dehydrated alcohol, activated carbon black is added to anhydrous
In ethyl alcohol, the alcohol suspending liquid containing activated carbon black is made.Alcohol suspending liquid and Nafion solution according still further to activated carbon black
Percent by volume is the ratio of 1:100, and Nafion solution is added, and ultrasonic disperse 20min forms carbon slurry.
Third step, the preparation of working electrode
It drips on the nickel foam substrate surface handled well according to the above-mentioned carbon slurry 160 μ L every square centimeter that pipette, is steamed to ethyl alcohol
After distributing, by electrode in 20 DEG C of vacuum drying 2h, used working electrode during pulse electrodeposition is made.
4th step prepares PtRu plating solution
By Pt salt Pt (acac)2, the second component metals salt Ru (acac)3, lauryl sodium sulfate be added to deionized water
In, at 20 °C, is made it completely dissolved after reaction 4h is sufficiently stirred, obtain PtRu alloy electroplating bath.The Pt salt and
The molar ratio of two component metals Ru salt is 1:60.The concentration of Pt salt is 0.005mol/L in PtRu alloy electroplating bath, additive
Concentration is 0.002mol/L, and the concentration of the metal salt of the second component is 0.3mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, by the prepared PtRu plating solution of the 4th step
It being placed in supersonic generator, supersonic frequency is set as 20kHz, and ultrasonic power is set as 10W, pulse electrodeposition is carried out,
Pulse current density is 1mAcm-2, electric current make-and-break time ratio ton/toffUnder conditions of being 30 DEG C for 0.3, temperature, electro-deposition
25s.The PtRu/C catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold air drying.Pulse electricity
Argon gas is first passed through into solution before deposition, to eliminate the influence of dissolved oxygen.
Embodiment 2: pulse electrodeposition prepares PtPd/C catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (oil removing, activation, washing, drying etc.) is successively carried out to Copper substrate material.
Second step prepares carbon material suspension
It prepares carbon slurry: the ratio of 4mg activated carbon black being added according to every milliliter of dehydrated alcohol, active carbon is added to anhydrous second
In alcohol, the alcohol suspending liquid containing activated carbon black is made.The body of alcohol suspending liquid and Nafion solution according still further to activated carbon black
The ratio that product percentage is 2:100, is added Nafion solution, and ultrasonic disperse 40min forms carbon slurry.
Third step, the preparation of working electrode
It is dripped on the Copper substrate surface handled well according to the above-mentioned carbon slurry living 105 μ L every square centimeter that pipette, to ethanol evaporation
After complete, by electrode in 40 DEG C of vacuum drying 4h, used working electrode during pulse electrodeposition is made.
4th step prepares PtPd plating solution
By Pt salt K2(PtCl4), the second component metals salt Na2PdCl6, neopelex be added to deionized water
In, under the conditions of 30 DEG C, is made it completely dissolved after reaction 5h is sufficiently stirred, obtain PtPd alloy electroplating bath.The Pt salt and
The molar ratio of two component metals Pd salt is 60:1.In PtPd alloy electroplating bath the concentration of Pt salt be 0.06mol/L, additive it is dense
Degree is 0.01mol/L, and the concentration of the Pd metal salt of the second component is 0.001mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, by the prepared PtPd plating solution of the 4th step
It being placed in supersonic generator, supersonic frequency is set as 90kHz, and ultrasonic power is set as 100W, pulse electrodeposition is carried out,
Pulse current density is 5mAcm-2, electric current make-and-break time ratio ton/toffUnder conditions of being 60 DEG C for 1, temperature, electro-deposition
60s.The PtPd/C catalyst that electro-deposition obtains successively is used into distilled water, ethyl alcohol clean the surface, and cold air drying.Pulse electrodeposition
Preceding elder generation is passed through argon gas into solution, to eliminate the influence of dissolved oxygen.
Embodiment 3: pulse electrodeposition prepares PtAg/C catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (oil removing, activation, washing, drying etc.) is successively carried out to iron matrix material.
Second step prepares carbon material suspension
It prepares carbon slurry: the ratio of 8mg activated carbon black being added according to every milliliter of dehydrated alcohol, active carbon is added to anhydrous second
In alcohol, the alcohol suspending liquid containing activated carbon black is made.The body of alcohol suspending liquid and Nafion solution according still further to activated carbon black
The ratio that product percentage is 4:100, is added Nafion solution, and ultrasonic disperse 80min forms carbon slurry.
Third step, the preparation of working electrode
It is dripped on the iron matrix surface handled well according to the above-mentioned carbon slurry 300 μ L every square centimeter that pipette, it is complete to ethanol evaporation
Afterwards, used working electrode during pulse electrodeposition is made in 70 DEG C of vacuum drying 5h in electrode.
4th step prepares PtAg plating solution
By Pt salt H2Pt(NO2)6·SO4, the second component metals salt AgNO3, polyethylene glycol be added in alcohol solvent, 40
Under the conditions of DEG C, is made it completely dissolved after reaction 10h is sufficiently stirred, obtain PtAg alloy electroplating bath.The Pt salt and the second component
The molar ratio of metal Ag salt is 10:1.The concentration of Pt salt is 0.5mol/L in PtAg alloy electroplating bath, and the concentration of additive is
0.03mol/L, the concentration of the Ag metal salt of the second component are 0.05mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, by the prepared PtAg plating solution of the 4th step
It being placed in supersonic generator, supersonic frequency is set as 160kHz, and ultrasonic power is set as 500W, pulse electrodeposition is carried out,
It is 10mAcm in pulse current density-2, electric current make-and-break time ratio ton/toffUnder conditions of being 50 DEG C for 1.5, temperature, electricity
Deposit 120s.The PtAg/C catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold air drying.
Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
Embodiment 4: pulse electrodeposition prepares PtNi/CNTs catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (oil removing, washing, drying etc.) is successively carried out to glass carbon matrix material.
Second step prepares carbon material suspension
Preparation carbon nanotube suspension: 5% Nafion solution is mixed with dehydrated alcohol according to the volume ratio of 1:9
It is even, carbon nanotube is added according to the ratio that 8mg carbon nanotube is added in every milliliter of dispersion liquid, ultrasonic disperse 20min forms carbon nanometer
Pipe suspension.
Third step, the preparation of working electrode
It pipettes above-mentioned 280 μ L of carbon nanotube suspension according to every square centimeter and drips on the glass carbon base body surface handled well,
After ethanol evaporation is complete, by electrode in 80 DEG C of vacuum drying 10h, used working electrode during pulse electrodeposition is made.
4th step prepares PtNi plating solution
By Pt salt H2PtCl6·6H2O, the second component metals salt NiCl2·6H2O is added in Reline ionic liquid,
Under the conditions of 50 DEG C, is made it completely dissolved after reaction 12h is sufficiently stirred, obtain PtNi alloy electroplating bath.The Pt salt and second group
The molar ratio for dividing W metal salt is 1:10.The concentration of Pt salt is 0.01mol/L in PtNi alloy electroplating bath, and the concentration of additive is
0.05mol/L, the concentration of the Ni metal salt of the second component are 0.1mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, by the prepared PtNi plating solution of the 4th step
It being placed in supersonic generator, supersonic frequency is set as 110kHz, and ultrasonic power is set as 900W, pulse electrodeposition is carried out,
It is 20mAcm in pulse current density-2, electric current make-and-break time ratio ton/toffUnder conditions of being 70 DEG C for 2, temperature, electricity is heavy
Product 350s.The PtNi/CNTs catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold air drying.
Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
Embodiment 5: pulse electrodeposition prepares PtFe/CNTs catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (oil removing, washing, drying etc.) is successively carried out to glass carbon matrix material.
Second step prepares carbon material suspension
Preparation carbon nanotube suspension: 5% Nafion solution is mixed with dehydrated alcohol according to the volume ratio of 1:9
It is even, carbon nanotube is added according to the ratio that 4mg carbon nanotube is added in every milliliter of dispersion liquid, ultrasonic disperse 20min forms carbon nanometer
Pipe suspension.
Third step, the preparation of working electrode
It pipettes above-mentioned 195 μ L of carbon nanotube suspension according to every square centimeter and drips on the glass carbon base body surface handled well,
After ethanol evaporation is complete, by electrode in 70 DEG C of vacuum drying 12h, used working electrode during pulse electrodeposition is made.
4th step prepares PtFe plating solution
By Pt salt K2PtCl6, the second component metals salt Fe (acac)3, hexadecyltrimethylammonium chloride be added to methanol
In, under the conditions of 60 DEG C, is made it completely dissolved after reaction 13h is sufficiently stirred, obtain PtFe alloy electroplating bath.The Pt salt and
The molar ratio of two component metals Fe salt is 71:1.The concentration of Pt salt is 1mol/L, the concentration of additive in PtFe alloy electroplating bath
For 0.08mol/L, the concentration of the Fe metal salt of the second component is 0.014mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, by the prepared PtFe plating solution of the 4th step
It being placed in supersonic generator, supersonic frequency is set as 75kHz, and ultrasonic power is set as 1100W, pulse electrodeposition is carried out,
It is 30mAcm in pulse current density-2, electric current make-and-break time ratio ton/toffUnder conditions of being 70 DEG C for 3.5, temperature, electricity
Deposit 380s.The PtFe/C catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold air drying.
Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
Embodiment 6: pulse electrodeposition prepares PtCo/CNTs catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (activation, washing, drying etc.) is successively carried out to carbon paper substrate material.
Second step prepares carbon material suspension
Preparation carbon nanotube suspension: 5% Nafion solution is mixed with dehydrated alcohol according to the volume ratio of 1:9
It is even, carbon nanotube is added according to the ratio that 8mg carbon nanotube is added in every milliliter of dispersion liquid, ultrasonic disperse 40min forms carbon nanometer
Pipe suspension.
Third step, the preparation of working electrode
It pipettes above-mentioned 110 μ L of carbon nanotube suspension according to every square centimeter and drips on the carbon paper substrate surface handled well,
After ethanol evaporation is complete, by electrode in 80 DEG C of vacuum drying 14h, used working electrode during pulse electrodeposition is made.
4th step prepares PtCo plating solution
By Pt salt Pt (NO2)2(NH3)2, the second component metals salt CoCl2·6H2O, cetyl trimethylammonium bromide is to second
In alcoholic solvent, under the conditions of 70 DEG C, is made it completely dissolved after reaction 18h is sufficiently stirred, obtain PtCo alloy electroplating bath.The Pt
The molar ratio of salt and the second component metals Co salt is 1:40.The concentration of Pt salt is 0.05mol/L, addition in PtCo alloy electroplating bath
The concentration of agent is 0.008mol/L, and the concentration of the Co metal salt of the second component is 2mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, by the prepared PtCo plating solution of the 4th step
It being placed in supersonic generator, supersonic frequency is set as 170kHz, and ultrasonic power is set as 1500W, pulse electrodeposition is carried out,
It is 50mAcm in pulse current density-2, electric current make-and-break time ratio ton/toffUnder conditions of being 80 DEG C for 4.5, temperature, electricity
Deposit 400s.The PtCo/CNTs catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold air drying
It is dry.Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
Embodiment 7: pulse electrodeposition prepares PtNiCo/CNTs catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (activation, washing, drying etc.) is successively carried out to carbon paper substrate material.
Second step prepares carbon material suspension
Preparation carbon nanotube suspension: 5% Nafion solution is mixed with dehydrated alcohol according to the volume ratio of 1:9
It is even, carbon nanotube is added according to the ratio that 15mg carbon nanotube is added in every milliliter of dispersion liquid, ultrasonic disperse 80min forms carbon and receives
Mitron suspension.
Third step, the preparation of working electrode
It pipettes above-mentioned 145 μ L of carbon nanotube suspension according to every square centimeter and drips on the carbon paper substrate surface handled well,
After ethanol evaporation is complete, by electrode in 70 DEG C of vacuum drying 16h, used working electrode during pulse electrodeposition is made.
4th step prepares PtNiCo plating solution
By Pt salt H2Pt(NO2)6·SO4, the second component metals salt Ni (NO3)2·6H2O、Co(NO3)2·6H2O, polyethylene
Pyrrolidones is added in ionic liquid tributyl-methyl phosphonium ammonium diimine salt, under the conditions of 80 DEG C, is made after reaction 19h is sufficiently stirred
It is completely dissolved, and obtains PtNiCo alloy electroplating bath.The molar ratio of the Pt salt and the second component metals Ni, Co salt is 1:
50:50.The concentration of Pt salt is 0.07mol/L in PtNiCo alloy electroplating bath, and the concentration of additive is 0.012mol/L, the second component
The concentration of Ni metal salt be the concentration of 3.5mol/L, Co metal salt be 3.5mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, and the prepared PtNiCo of the 4th step is plated
Liquid is placed in supersonic generator, and supersonic frequency is set as 130kHz, and ultrasonic power is set as 1800W, and it is heavy to carry out pulse electricity
Product is 55mAcm in pulse current density-2, electric current make-and-break time ratio ton/toffFor 4, it is at a temperature of 90 °C under the conditions of, electricity
Sedimentation time 500s.The PtNiCo/GNTs catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and
Cold air drying.Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
Embodiment 8: pulse electrodeposition prepares PtPdCu/CNTs catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (activation, washing, drying etc.) is successively carried out to carbon cloth basis material.
Second step prepares carbon material suspension
Preparation carbon nanotube suspension: 5% Nafion solution is mixed with dehydrated alcohol according to the volume ratio of 1:9
It is even, carbon nanotube is added according to the ratio that 20mg carbon nanotube is added in every milliliter of dispersion liquid, ultrasonic disperse 100min forms carbon and receives
Mitron suspension.
Third step, the preparation of working electrode
It pipettes above-mentioned 175 μ L of carbon nanotube suspension according to every square centimeter and drips on the carbon cloth matrix surface handled well,
After ethanol evaporation is complete, by electrode in 80 DEG C of vacuum drying 18h, used working electrode during pulse electrodeposition is made.
4th step prepares PtPdCu plating solution
By Pt salt K2Pt(OH)6, the second component metals salt Na2PdCl4、CuCl2, octyl phenol polyoxyethylene ether be added to ion
Liquid [BMIM] PF6In, under the conditions of 90 DEG C, is made it completely dissolved after reaction 20h is sufficiently stirred, obtain PtPdCu Alloy Plating
Liquid.The molar ratio of the Pt salt and the second component metals Pd, Cu salt is 40:1:1.Pt salt is dense in PtPdCu alloy electroplating bath
Degree is 0.04mol/L, and the concentration of additive is 0.003mol/L, the concentration of the Pd metal salt of the second component be 0.001mol/L,
The concentration of Cu metal salt is 0.001mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, and the prepared PtPdCu of the 4th step is plated
Liquid is placed in supersonic generator, and supersonic frequency is set as 195kHz, and ultrasonic power is set as 1900W, and it is heavy to carry out pulse electricity
Product is 70mAcm in pulse current density-2, electric current make-and-break time ratio ton/toffUnder conditions of being 80 DEG C for 5, temperature, electricity
Deposit 1000s.The PtPdCu/CNTs catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold wind
It is dry.Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
Embodiment 9: pulse electrodeposition prepares PtB/Gr catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (oil removing, activation, washing, drying etc.) is successively carried out to graphite substrate material.
Second step prepares carbon material suspension
It prepares graphene suspension: the Nafion solution of volume fraction 5% and dehydrated alcohol is mixed according to the volume ratio of 1:9
Conjunction is formed uniformly dispersion liquid, is added graphene according to the ratio that 4mg graphene is added in every milliliter of dispersion liquid, ultrasonic disperse 30min,
Form graphene suspension.
Third step, the preparation of working electrode
It pipettes above-mentioned 125 μ L of Activated Graphite alkene suspension according to every square centimeter and drips to the graphite matrix surface handled well
On, after ethanol evaporation is complete, by electrode in 90 DEG C of vacuum drying 20h, used work electricity during pulse electrodeposition is made
Pole.
4th step prepares PtB plating solution
By Pt salt H2PtCl6·6H2O, the second component non-metal salt dimethylamino borine, succimide be added to from
In sub- water, under the conditions of 100 DEG C, is made it completely dissolved after reaction 20h is sufficiently stirred, obtain PtB plating solution.The Pt salt and
The molar ratio of the nonmetallic B salt of two components is 5:1.The concentration of Pt salt is 1mol/L in PtB alloy electroplating bath, and the concentration of additive is
The concentration of 0.07mol/L, B non-metal salt is 0.45mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, and the prepared PtB plating solution of the 4th step is put
It being placed in supersonic generator, supersonic frequency is set as 155kHz, and ultrasonic power is set as 2100W, pulse electrodeposition is carried out,
Pulse current density is 80mAcm-2, electric current make-and-break time ratio ton/toffUnder conditions of being 80 DEG C for 5.6, temperature, electricity is heavy
Product 3000s.The PtB/Gr catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold air drying.Arteries and veins
Argon gas is first passed through into solution before rushing electro-deposition, to eliminate the influence of dissolved oxygen.
Embodiment 10: pulse electrodeposition prepares PtPdCu/Gr catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (oil removing, activation, washing, drying etc.) is successively carried out to electro-conductive glass basis material.
Second step prepares carbon material suspension
It prepares graphene suspension: the Nafion solution of volume fraction 5% and dehydrated alcohol is mixed according to the volume ratio of 1:9
Conjunction is formed uniformly dispersion liquid, is added graphene according to the ratio that 8mg graphene is added in every milliliter of dispersion liquid, ultrasonic disperse 50min,
Form graphene suspension.
Third step, the preparation of working electrode
It pipettes above-mentioned 340 μ L of Activated Graphite alkene suspension according to every square centimeter and drips to the electro-conductive glass matrix table handled well
On face, after ethanol evaporation is complete, by electrode in 100 DEG C of vacuum drying 21h, used work during pulse electrodeposition is made
Electrode.
4th step prepares PtPdCu/Gr plating solution
By Pt salt K2PtCl4, the second component metal salt Na2PdCl4、CuCl2, polyethylene glycol be added [Bu3MeN][N
(CF3SO2)2] in ionic liquid, under the conditions of 90 DEG C, 20h is sufficiently stirred, and it is completely dissolved, and obtains PtPdCu alloy electroplating bath.Institute
The Pt salt stated, Pd salt, Cu metal salt molar ratio be 6:1:1.The concentration of Pt salt is 0.12mol/ in PtPdCu alloy electroplating bath
L, the concentration of additive are 0.01mol/L, and the concentration of Pd metal salt is 0.02mol/L, and the concentration of Cu metal salt is 0.02mol/
L。
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, and the prepared PtPdCu of the 4th step is plated
Liquid is placed in supersonic generator, and supersonic frequency is set as 40kHz, and ultrasonic power is set as 2500W, and it is heavy to carry out pulse electricity
Product is 90mAcm in pulse current density-2, electric current make-and-break time ratio ton/toffUnder conditions of being 80 DEG C for 6, temperature, electricity
Deposit 4000s.The PtPdCu/Gr catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold air drying
It is dry.Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
Embodiment 11: pulse electrodeposition prepares PtNiCo/Gr catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (oil removing, activation, washing, drying etc.) is successively carried out to electro-conductive glass basis material.
Second step prepares carbon material suspension
It prepares graphene suspension: the Nafion solution of volume fraction 5% and dehydrated alcohol is mixed according to the volume ratio of 1:9
Conjunction is formed uniformly dispersion liquid, and graphene, ultrasonic disperse is added according to the ratio that 15mg graphene is added in every milliliter of dispersion liquid
80min forms graphene suspension.
Third step, the preparation of working electrode
It pipettes above-mentioned 220 μ L of graphene suspension according to every square centimeter and drips to the electro-conductive glass matrix surface handled well
On, after ethanol evaporation is complete, by electrode in 90 DEG C of vacuum drying 22h, used work electricity during pulse electrodeposition is made
Pole.
4th step prepares PtNiCo plating solution
By Pt salt Na2Pt(OH)6, the second component metal salt Ni (NO3)2·6H2O、Co(NO3)2·6H2O, oleic acid is added
Into ethyl alcohol, under the conditions of 100 DEG C, 22h is sufficiently stirred, and it is completely dissolved, and obtains PtNiCo alloy electroplating bath.The Pt salt, Ni
Salt, Co metal salt molar ratio be 16:1:1.In PtNiCo alloy electroplating bath the concentration of Pt salt be 0.8mol/L, additive it is dense
Degree is 0.05mol/L, and the concentration of Ni metal salt is 0.15mol/L, and the concentration of Co metal salt is 0.15mol/L.
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, and the prepared PtNiCo of the 4th step is plated
Liquid is placed in supersonic generator, and supersonic frequency is set as 185kHz, and ultrasonic power is set as 2600W, and it is heavy to carry out pulse electricity
Product is 90mAcm in pulse current density-2, electric current make-and-break time ratio ton/toffFor 6, it is at a temperature of 90 °C under the conditions of, electricity
Deposit 5000s.The PtNiCo/Gr catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold air drying
It is dry.Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
Embodiment 12: pulse electrodeposition prepares PtNiP/Gr catalyst under ultrasound condition:
The first step, substrate material surface pretreatment
Pre-treatment (oil removing, activation, washing, drying etc.) is successively carried out to electro-conductive glass basis material.
Second step prepares carbon material suspension
It prepares graphene suspension: the Nafion solution of volume fraction 5% and dehydrated alcohol is mixed according to the volume ratio of 1:9
Conjunction is formed uniformly dispersion liquid, and graphene, ultrasonic disperse is added according to the ratio that 20mg graphene is added in every milliliter of dispersion liquid
100min forms graphene suspension.
Third step, the preparation of working electrode
It pipettes above-mentioned 235 μ L of graphene suspension according to every square centimeter and drips to the electro-conductive glass matrix surface handled well
On, after ethanol evaporation is complete, for 24 hours in 80 DEG C of vacuum drying by electrode, used work electricity during pulse electrodeposition is made
Pole.
4th step prepares PtNiP plating solution
By Pt salt H2PtCl6·6H2O, metal salt NiCl2·6H2O, non-metal salt NaH2PO2·H2O, niacinamide is added
EMI-Cl-BF4In ionic liquid, under the conditions of 70 DEG C, be sufficiently stirred for 24 hours its be completely dissolved, obtain PtNiP alloy electroplating bath.Institute
The Pt salt stated, Ni salt, P non-metal salt molar ratio be 9:80:16.The concentration of Pt salt is in PtNiP alloy electroplating bath
0.45mol/L, the concentration of additive are 0.01mol/L, and the concentration of Ni metal salt is 4mol/L, and the concentration of P non-metal salt is
0.8mol/L。
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, by the prepared PtNiP plating solution of the 4th step
It being placed in supersonic generator, supersonic frequency is set as 60kHz, and ultrasonic power is set as 2900W, pulse electrodeposition is carried out,
It is 100mAcm in pulse current density-2, electric current make-and-break time ratio ton/toffFor 6, it is at a temperature of 90 °C under the conditions of, electricity is heavy
Product 7000s.The PtNiP/Gr catalyst that electro-deposition obtains successively is used into distilled water, washes of absolute alcohol surface, and cold air drying.
Argon gas is passed through before pulse electrodeposition, into solution first to eliminate the influence of dissolved oxygen.
Embodiment described above only expresses embodiments of the present invention, and but it cannot be understood as to the invention patent
Range limitation, it is noted that for those skilled in the art, without departing from the inventive concept of the premise, also
Several modifications and improvements can be made, these are all belonged to the scope of protection of the present invention.
Claims (10)
1. a kind of method that pulse electrodeposition prepares Pt base catalyst under ultrasound condition, it is characterised in that following steps:
The first step, substrate material surface pretreatment
Second step, prepares carbon material suspension, and carbon material includes activated carbon black, carbon nanotube or graphene
It prepares carbon slurry: the ratio of 1~10mg activated carbon black being added according to every milliliter of dehydrated alcohol, activated carbon black is added to anhydrous
In ethyl alcohol, the alcohol suspending liquid containing activated carbon black is made；Alcohol suspending liquid and Nafion solution according still further to activated carbon black
Percent by volume is the ratio of 1:100~6:100, and Nafion solution 10~120min of ultrasonic disperse of volume fraction 5% is added,
Form carbon slurry；
Preparation carbon nanotube suspension: the Nafion solution of volume fraction 5% is mixed with dehydrated alcohol according to the volume ratio of 1:9
Uniformly, carbon nanotube is added according to the ratio that 1~20mg carbon nanotube is added in every milliliter of dispersion liquid, ultrasonic disperse 10~
120min forms carbon nanotube suspension；
It prepares graphene suspension: the Nafion solution of volume fraction 5% is mixed with dehydrated alcohol according to the volume ratio of 1:9
It is even, graphene is added according to the ratio that 1~20mg graphene is added in every milliliter of dispersion liquid, 10~120min of ultrasonic disperse is formed
Graphene suspension；
Third step, preparation work electrode
One of carbon slurry, carbon nanotube or suspension of graphene are added drop-wise on the catalyst matrix surface handled well, often
The carbon material of 100~350 μ L is added dropwise in square centimeter；After matrix surface ethyl alcohol evaporating completely, matrix is dried in vacuo, arteries and veins is made
Rush working electrode used in electrodeposition process；
4th step prepares Pt base catalyst plating solution
Pt salt, the second component salt (metal salt or non-metal salt), additive are added in solvent, under the conditions of 20~100 DEG C,
Reaction 1~make it completely dissolved afterwards for 24 hours is sufficiently stirred, obtains Pt base catalyst plating solution；The Pt salt and the second component metals
Or the molar ratio of non-metal salt is 1:80~80:1；The concentration of Pt salt is 0.001~1mol/L in Pt base catalyst plating solution, is added
The concentration for adding agent is 0~0.1mol/L, and the concentration of the metal salt of the second component is 0~5mol/L, the non-metal salt of the second component
Concentration be 0~1mol/L；
5th step carries out pulse electrodeposition under ultrasound condition
Using working electrode made from third step as cathode, graphite rod is anode, in the supersonic frequency of 20~200kHz, 0~
Under the ultrasonic power of 3000W, pulse electrodeposition, pulse current density are carried out in the prepared Pt base catalyst plating solution of the 4th step
For 0.1~100mAcm-2, the make-and-break time ratio t of electric currenton/toffIt is 0.3~6, temperature is 20~100 DEG C, sedimentation time 1
~7200s；The Pt base catalyst that electro-deposition obtains successively is used into dehydrated alcohol, distilled water clean the surface, and cold air drying；Pulse
Argon gas is passed through before electro-deposition, into solution first to eliminate the influence of dissolved oxygen.
2. the method that pulse electrodeposition prepares Pt base catalyst under a kind of ultrasound condition according to claim 1, feature
It is, the Pt salt includes H2PtCl6·6H2O、K2(PtCl4)、K2PtCl6、Pt(acac)2、Pt(NO2)2(NH3)2、H2Pt
(NO2)2SO4、Na2Pt(OH)6And K2Pt(OH)6。
3. the method that pulse electrodeposition prepares Pt base catalyst under a kind of ultrasound condition according to claim 1 or 2, special
Sign is that the solvent in the 4th step includes aqueous solution, organic solvent, ionic liquid；Wherein organic solvent include methanol,
The alcohols such as ethyl alcohol；Ionic liquid include containing alkyl quaternary ammonium ion, alkyl quaternary alkylphosphonium salt ion, dialkyl group replace imidazol ion and
The ionic liquid of the alkyl-substituted pyridinium ion cation of N- and contain PF6 -、BF4 -、[N(CFSO2)]-、CF3SO3 -、AlCl4 -、
CF3COO-、SbF6 -、Cl-、Br-、I-、NO3 -、ClO4 -Anion ion liquid.
4. the method that pulse electrodeposition prepares Pt base catalyst under a kind of ultrasound condition according to claim 1 or 2, special
Sign is, second component element includes non-platinum noble metals, transition metal or one of nonmetallic or multiple element；Its
In, the non-platinum noble metals include Rh, Ru, Pd, Au, Ag, and the transition metal includes Fe, Co, Ni, Cu etc., described
Nonmetallic includes B, C, P, S, N.
5. the method that pulse electrodeposition prepares Pt base catalyst under a kind of ultrasound condition according to claim 3, feature
It is, second component element includes non-platinum noble metals, transition metal or one of nonmetallic or multiple element；Its
In, the non-platinum noble metals include Rh, Ru, Pd, Au, Ag, and the transition metal includes Fe, Co, Ni, Cu etc., described
Nonmetallic includes B, C, P, S, N.
6. the method that pulse electrodeposition prepares Pt base catalyst under a kind of ultrasound condition described according to claim 1 or 2 or 5,
It is characterized in that, the additive includes lauryl sodium sulfate, neopelex, sodium glycocholate, dioctyl amber
Amber disulfonate acid, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, polyethylene glycol, polyvinyl alcohol, butine two
Alcohol, oleic acid, succimide, niacinamide, polyethyleneimine, polyvinylpyrrolidone, octyl phenol polyoxyethylene ether, alkyl fatty
Alcohol polyoxyethylene ether, aliphatic amine polyoxyethylene ether, alkylol phthalein amine polyoxyethylene ether one or more arbitrary proportion mixture.
7. the method that pulse electrodeposition prepares Pt base catalyst under a kind of ultrasound condition according to claim 3, feature
It is, the additive includes lauryl sodium sulfate, neopelex, sodium glycocholate, dioctyl succinate acid sulphur
Sour sodium, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, polyethylene glycol, polyvinyl alcohol, butynediols, oil
Acid, succimide, niacinamide, polyethyleneimine, polyvinylpyrrolidone, octyl phenol polyoxyethylene ether, alkyl alcohol are poly-
Ethylene oxide ether, aliphatic amine polyoxyethylene ether, alkylol phthalein amine polyoxyethylene ether one or more arbitrary proportion mixture.
8. the method that pulse electrodeposition prepares Pt base catalyst under a kind of ultrasound condition according to claim 4, feature
It is, the additive includes lauryl sodium sulfate, neopelex, sodium glycocholate, dioctyl succinate acid sulphur
Sour sodium, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, polyethylene glycol, polyvinyl alcohol, butynediols, oil
Acid, succimide, niacinamide, polyethyleneimine, polyvinylpyrrolidone, octyl phenol polyoxyethylene ether, alkyl alcohol are poly-
Ethylene oxide ether, aliphatic amine polyoxyethylene ether, alkylol phthalein amine polyoxyethylene ether one or more arbitrary proportion mixture.
9. pulse electrodeposition prepares Pt base catalyst under a kind of ultrasound condition described according to claim 1 or 2 or 5 or 7 or 8
Method, which is characterized in that vacuum drying temperature in the third step is 20~100 DEG C, the time is 1~for 24 hours.
10. the method that pulse electrodeposition prepares Pt base catalyst under a kind of ultrasound condition according to claim 6, feature
Be, the vacuum drying temperature in the third step be 20~100 DEG C, the time be 1~for 24 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112423A (en) * | 2019-04-08 | 2019-08-09 | 华南理工大学 | A kind of microchannel recycle stream dynamic formula pulse electrodeposition device being used to prepare platinum base catalyst with core-casing structure and its application method |
| CN110277565A (en) * | 2019-05-28 | 2019-09-24 | 南方科技大学 | Platinum-indium catalyst for fuel cell and preparation method and application thereof |
| CN110323459A (en) * | 2019-06-23 | 2019-10-11 | 华北电力大学 | A kind of noble metal base nano-catalyst of the growth in situ on carrier and preparation method thereof |
| CN111545219A (en) * | 2020-05-01 | 2020-08-18 | 赵玉平 | Catalyst for preparing acrolein by propylene oxidation and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0230790A (en) * | 1988-07-15 | 1990-02-01 | Seiko Instr Inc | Method for electrodepositing alloy |
| CN1947835A (en) * | 2006-09-12 | 2007-04-18 | 北京科技大学 | Pulse electrodeposition method for producing catalyst for direct methanol fuel cell |
| US7635461B2 (en) * | 2003-06-06 | 2009-12-22 | University Of Utah Research Foundation | Composite combustion catalyst and associated methods |
| CN101728541A (en) * | 2008-10-17 | 2010-06-09 | 北京化工大学 | Method for preparing carbon nano tube loaded cobalt-platinum alloy catalyst |
| CN102002748A (en) * | 2010-12-09 | 2011-04-06 | 大连大学 | Method for preparing ferromagnetic nano composite material with pulse-ultrasound electrodeposition |
| CN103628106A (en) * | 2013-11-01 | 2014-03-12 | 大连理工大学 | Method for preparing indium/tellurium porous nanowire array |
| CN108110284A (en) * | 2016-11-18 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method for directly preparing fuel cell Pt nanocrystal nucleocapsid Catalytic Layer |
-
2018
- 2018-10-29 CN CN201811264623.4A patent/CN109331820A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0230790A (en) * | 1988-07-15 | 1990-02-01 | Seiko Instr Inc | Method for electrodepositing alloy |
| US7635461B2 (en) * | 2003-06-06 | 2009-12-22 | University Of Utah Research Foundation | Composite combustion catalyst and associated methods |
| CN1947835A (en) * | 2006-09-12 | 2007-04-18 | 北京科技大学 | Pulse electrodeposition method for producing catalyst for direct methanol fuel cell |
| CN101728541A (en) * | 2008-10-17 | 2010-06-09 | 北京化工大学 | Method for preparing carbon nano tube loaded cobalt-platinum alloy catalyst |
| CN102002748A (en) * | 2010-12-09 | 2011-04-06 | 大连大学 | Method for preparing ferromagnetic nano composite material with pulse-ultrasound electrodeposition |
| CN103628106A (en) * | 2013-11-01 | 2014-03-12 | 大连理工大学 | Method for preparing indium/tellurium porous nanowire array |
| CN108110284A (en) * | 2016-11-18 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method for directly preparing fuel cell Pt nanocrystal nucleocapsid Catalytic Layer |
Non-Patent Citations (1)
| Title |
|---|
| FEI XIAO ET AL.: "Nonenzymatic glucose sensor based on ultrasonic-electrodeposition of bimetallic PtM (M= Ru, Pd and Au) nanoparticles on carbon nanotubes-ionic liquid composite film", 《BIOSENSORS AND BIOELECTRONICS》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112423A (en) * | 2019-04-08 | 2019-08-09 | 华南理工大学 | A kind of microchannel recycle stream dynamic formula pulse electrodeposition device being used to prepare platinum base catalyst with core-casing structure and its application method |
| CN110112423B (en) * | 2019-04-08 | 2024-02-09 | 华南理工大学 | Microchannel circulating flow type pulse electrodeposition device for preparing platinum-based core-shell structure catalyst and application method thereof |
| US11196056B2 (en) | 2019-05-28 | 2021-12-07 | Southern University Of Science And Technology | Platinum-indium cluster catalyst for fuel cell, method for preparing the same, and method for using the same |
| CN110277565A (en) * | 2019-05-28 | 2019-09-24 | 南方科技大学 | Platinum-indium catalyst for fuel cell and preparation method and application thereof |
| CN110323459A (en) * | 2019-06-23 | 2019-10-11 | 华北电力大学 | A kind of noble metal base nano-catalyst of the growth in situ on carrier and preparation method thereof |
| CN110323459B (en) * | 2019-06-23 | 2020-09-18 | 华北电力大学 | Noble metal-based nano catalyst growing in situ on carrier and preparation method thereof |
| CN111545219A (en) * | 2020-05-01 | 2020-08-18 | 赵玉平 | Catalyst for preparing acrolein by propylene oxidation and preparation method thereof |
| CN111740122B (en) * | 2020-07-06 | 2021-12-28 | 全球能源互联网研究院有限公司 | Ordered membrane electrode and preparation method thereof |
| CN111740122A (en) * | 2020-07-06 | 2020-10-02 | 全球能源互联网研究院有限公司 | Ordered membrane electrode and preparation method thereof |
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Application publication date: 20190215 |